Process of converting gaseous hydrocarbon material into normally liquid hydrocarbon material



INVENTOR.`

ffm N@ BY W f ATToRNEYs.

Patented June 20, 1939 UNITED STATES yPATENT oFFicE James R. Rose, Edgeworth, Pa.

Application November 22, 1937, Serial No. 175,886 f 3 Claims.

This invention relates to a process of converting normally gaseous hydrocarbon material into normally liquid hydrocarbon material, and has particular reference to the treatment of petro- :s leurn refinery gases for the conversion thereof into liquid hydrocarbon material in the nature of gasolene.

The principal object of the invention is to provide for obtaining greater yields of liquid material than has heretofore been possible.

I accomplish the above and other and more limited objects by the process and 'by the use of the preferred apparatus hereinafter described and illustrated in the drawing, wherein thfv 'figure l5 is a flow diagram illustrating such preferred apparatus and the relation of the various pieces of such apparatus to one another.

- It is known that normally gaseous hydrocarbons produced in the refnement ofY petroleum 20 can be caused to condense or polymerize by sub- Jecting them to the action of a suitable catalyst in the gaseous state. I have discovered that the yield of liquid hydrocarbon can be greatly increased if these gases are first liquefied, by subject-ing them-to pressure at temperatures below their critical temperatures for liquefaction; are cracked by heat while being maintained under such pressure and the cracked product is thenv subjected to the catalyst specified herein `while under such pressure; and the pressure thereafter reduced to a working pressure of say 5 to 25 lbs. per square inch. I have discovered also that the particular catalyst set forth herein is also more effective than others that have been in general use for catalyzing the polymerization of these gases under usual conditions as well as being peculiarly effective under the conditions above set forth. Where my new process includes the use of my new catalyst, the yield is remarkably increased over that obtainable by other processes with which I am familiar. For example, by the combination of my new process and new catalyst, I have obtained an average yield from refinery gases of as much as 14 to 15 gallons per 1000 cu. ft. and from waste refinery gases an average yield of approximately 5 gallons per 1000 cu. ft., the product being of high gravity and octane numberranging betweenv 65 and 85 specific gravity and between 90 and 110 octane number, with an initial boiling point of from 60 to 70 F. and with an 80% recovery at 300 F. end point.

In the drawing, I have shown schematically one apparatus which may be used in carrying out my process. This apparatus is adapted for continuous operation and is only an example of divers forms of apparatus which Vmay beV em-vv ployed. The gaseous hydrocarbons are led through a pipe I0, meteriII and pipe I2 to an expansible gas lstorage tank I3. From the stor-v age tank I3. they are drawn off through a pipe I4 and passed through a cooling coil I5 which may be immersed in a cooling fluid contained in a receptacle I6. From the coil` I5, the so-cooled gases, which havebee'n cooled below the critical temperature for liquefaction, pass through a pipe 10 Il to the compressor I8 where they are Subjected to a pressure of from 500 to 1500 lbs. per square inch and from which they are delivered in liquid condition, or largely in liquid condition, through a pipe I9 to a liquid column holder 20 which may be provided with an inspection win- A dow v2l and a blow off valve 22 through which any unliquefied portion may be removed.

From the bottom of the holder 20, the liquefied. material passes througha pipe 23 to a coil 24 immersed in a heat absorbing and transferring fluid contained in a receptacle 25. The luidin the receptacle 25 is heated by means of the burner 26 and the whole is contained within an enclosure 21. By the time the liquefied material has passed through the coil 24,- it has assumed substantially the temperature of the fluid in the receptacle 25, which temperature is such as to crack the previously liquefied material. I 'prefer to use a temperature of from 500 to 1500 Fnat this point.

After having traversed the coil 2l, the cracked material passes through the catalyzing chamber 28, where it intimately contacts the catalyst contained therein. The vaporous material then passes to a blending and reaction tank 29, where the reaction initiated in the catalyst chamber may be continued. The size of the tank '29 will be so chosen as to permit continuation of the reaction during such time as the reaction proceeds at a sufliciently high rate to increase the yield to a substantial extent. From the chamber 29, the vaporous material passes to a cooler 30 where its temperature is reduced tobetween 50 and '75 F. and is again liquefied; and thence to a tank 3|, provided with a blow off valve 32. wherein the material which is of an intermediate nature between the liquid and the gaseous state, (such as heavy vapors or floating globules of liquid) may coalesce and unite with the body of liquid, while uncondensed gases unsuitable for recycling may be ventedthrough said valve.4 From the tank 3l the liquid may pass to an expansion valve or pressure relief valve 33, which preferably is in the nature of a variable restricpressure of the material is reduced to an ordinary mately as follows:

working pressure of say from to 25 lbs. per square inch and enters a low pressure receptacle 3l which is warmed by means of a suitable fluid contained in the receptacle 35 so as to overcome the cooling eii'ect induced by the escape of the liquid through the expansion valve 33.

In the receptacle 34, that portion of the material which has been converted 'into normally liquid hydrocarbon will remain liquid and pass through the pipe 36 to the storage tank 31. The portion which has not been sumciently polymerized to remain liquid under normal pressure and temperature conditions is re-cyc1ed,passing through the conduit`38 and entering the gas storage receptacle I3.

It will be noted that such gases as are not liqueable do not collect in the system but are liberated at the points 22 and 32, where they may be recovered for other uses if desired.

It will be noted also that between the compressor I8 and the expansion valve 33, the passage containing Vthe material being treated is under high pressure, the same being controlled by the capacity and rate of operation of the compressor I`8"and the adjustment of the expansion valve 33.' Within this region of the treatmentpassage, there are portions wherein the material being treated is liquid and a portion wherein it is in a vaporous condition, the difference in 4phase beingbrought about by the elevation of the temperature in the coil 24 and by the catalyzing chamber 28. Thus,'by suitable manipulation of the temperature and of the expansion valve 33, the pressure is maintained high throughout the region between the compressor I8 and the said valve and the material is nevertheless changed from liquid vphase to vapor phase and back again.

The catalyst which I prefer'to employ and which has proven to be peculiarly useful in connection with' this process is,of approximately the following composition:

. Parts by weight Natural phosphate rock 20 to 100 Carnotite ore 20 to 100 Zinc phosphate 5 to 20 Barium halide 3 to 12 The most advantageous proportion is approxi- Parts by weight Natural phosphate rock 40 Carnotite ore...A 40 Zinc phosphate Barium halide, preferably the ch1oride 6 Having thus described my invention, what I claim is: i

1. The process of manufacturing liquid hydrocarbons suitable for motor fuel from rei'inery gases containing saturates and unsaturates which comprises: liquefylng the said gases under a pressure of from 500 to 1500 pounds per square inch; heating the resultant liquid while under said pressure to a temperature of from 500 l". to l500 F., thereby to crack the same; contacting the resultant material, while under the said pressure, with a polymerization catalyst; cooling the resultant material to a temperature of from 50 F. to 75 F. while under the polymerization pressure; venting uncondensed gases from the system; and reducing the pressure on the resultant liquid, thereby to separate, from the liquid polymer, gases suitable for recycling; the said catalyst comprising the following ingredients in substantially the following proportions by weight l Parts Natural phosphate rock to 100 Carnotite ore 20 to 100 Zinc phosphate 5 to 20 Barium halide 3 to 12 2. In the process recitedin claim 1, the additional step of recycling the gases, suitable for recycling, which have been separated from the liquid polymer consequent upon the reductio in pressure upon the latter.

3. The process of manufacturing liquid hydrocarbons suitable for motor fuel from reilnery gases containing saturates and unsaturates which comprises: liquefying the said gases under a pressure of from 500 to 1500 pounds per square inch; heating the resultant liquid while under said pressure to a temperature of from 500 F. to 1500 F., thereby to crack the same; contacting the resultant material, while under the said pressure, with a polymerization catalyst; cooling the resultant material to a temperature oi' from 50 F. to 75 F. while under the polymerization pressure;l venting uncondensed gases from the system; and reducing the pressure on the result-f ant liquid, thereby to separate, from the liquid polymer, gases suitable for` recycling; recycling the gases thus separated from the liquid polymer; the said catalyst comprising the following ingredientsvin substantially the following proportions by weight:

Parts Natural phosphate rock 40 Carnotite ore 40 Zinc phosphate Barium chloride... 6

JAMES n. Rosa. 

